The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Vapor pressures and evaporation coefficients for melts of ferromagnesian chondrule-like compositions

To determine evaporation coefficients for the major gaseous species that evaporate from silicate melts, the Hertz-Knudsen equation was used to model the compositions of residues of chondrule analogs produced by evaporation in vacuum by Hashimoto [Hashimoto A. (1983) Evaporation metamorphism in the early solar nebula-evaporation experiments on the melt FeO-MgO-SiO₂-CaO-Al₂O₃ and chemical fractionations of primitive materials. Geochem. J. 17, 111-145] and Wang et al. [Wang J., Davis A. M., Clayton R. N., Mayeda T. K., Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO₂-CaO-Al₂O₃-TiO₂ rare earth element melt system. Geochim. Cosmochim. Acta 65, 479-494], in vacuum and in H₂ by Yu et al. [Yu Y., Hewins R. H., Alexander C. M. O’D., Wang J. (2003) Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts. Geochim. Cosmochim. Acta 67, 773-786], and in H₂ by Cohen et al. [Cohen B. A., Hewins R. H., Alexander C. M. O’D. (2004) The formation of chondrules by open-system melting of nebular condensates. Geochim. Cosmochim. Acta 68, 1661-1675]. Vapor pressures were calculated using the thermodynamic model of Ghiorso and Sack [Ghiorso M. S., Sack R. O. (1995) Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures. Contrib. Mineral. Petrol. 119, 197-212], except for the late, FeO-free stages of the Wang et al. (2001) and Cohen et al. (2004) experiments, where the CMAS activity model of Berman [Berman R. G. (1983) A thermodynamic model for multicomponent melts, with application to the system CaO-MgO-Al₂O₃-SiO₂. Ph.D. thesis, University of British Columbia] was used. From these vapor pressures, evaporation coefficients (α) were obtained that give the best fits to the time variation of the residue compositions. Evaporation coefficients derived for Fe_(g), Mg_(g), and SiO_(g) from the Hashimoto (1983) experiments are similar to those found by Alexander [Alexander C. M. O’D. (2004) Erratum. Meteoritics Planet. Sci. 39, 163] in his EQR treatment of the same data and also adequately describe the FeO-bearing stages of the Wang et al. (2001) experiments. From the Yu et al. (2003) experiments at 1723 K, α_Na = 0.26 ± 0.05, and α_K = 0.13 ± 0.02 in vacuum, and α_Na = 0.042 ± 0.020, andα_K = 0.017 ± 0.002 in 9 × 10⁻⁵ bar H₂. In the FeO-free stages of the Wang et al. (2001) experiments, α_Mg and α_SiO are significantly different from their respective values in the FeO-bearing portions of the same experiments and from the vacuum values obtained at the same temperature by Richter [Richter F. M., Davis A. M., Ebel D. S., Hashimoto A. (2002) Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta 66, 521-540] for CMAS compositions much lower in MgO. When corrected for temperature, the values of α_Mg and α_SiO that best describe the FeO-free stages of the Wang et al. (2001) experiments also adequately describe the FeO-free stage of the Cohen et al. (2004) H₂ experiments, but α_Fe that best describes the FeO-bearing stage of the latter experiment differs significantly from the temperature-corrected value derived from the Hashimoto (1983) vacuum data.     

Temperature and its control of isotope fractionation by a sulfate-reducing bacterium

A synthesis of previous results, which we dub the “standard model,” provides a prediction as to how isotope fractionation during sulfate reduction should respond to physiological variables such as specific rate of sulfate reduction and environmental variables such as substrate availability and temperature. The standard model suggests that isotope fractionation should decrease with increasing specific rates of sulfate reduction (rate per cell). Furthermore, the standard model predicts that low fractionations should be found at both high and low temperatures whereas the highest fractionations should be found in the intermediate temperature range. These fractionation trends are controlled, as a function of temperature, by the balance between the transfer rates of sulfate into and out of the cell and the exchange between the sulfur pools internal to the organism. We test this standard model by conducting experiments on the growth physiology and isotope fractionation, as a function of temperature, by the sulfate-reducing bacterium Desulfovibrio desulfuricans (DSMZ 642). Our results contrast with the “standard model” by showing a positive correlation between specific rates of sulfate reduction and fractionation. Also by contrast with the standard model, we found the highest fractionations at low and high temperatures and the lowest fractionations in the intermediate temperature range. We develop a fractionation model which can be used to explain both our results as well as the results of the “standard model.” Differences in fractionation with temperature relate to differences in the specific temperature response of internal enzyme kinetics as well as the exchange rates of sulfate in and out of the cell. It is expected that the kinetics of these processes will show strain-specific differences.     

Enamel diagenesis at South African Australopith sites: Implications for paleoecological reconstruction with trace elements

Elemental ratio data from archaeological and paleontological bone have often been used for paleoecological reconstruction, but recent studies have shown that, even when solubility profiling techniques are employed in an attempt to recover biogenic signals, bone is an unreliable material. As a result, there has been renewed interest in using enamel for such studies, as it is known to be less susceptible to diagenesis. Nevertheless, enamel is not immune from diagenetic processes, and several studies have suggested that paleoecologically relevant elements may be altered in fossil enamel. Here, we investigate Sr, Ba, Zn, and Pb compositions of enamel from South African karstic cave sites in an effort to ascertain whether or not this material provides reliable paleoecological information. We compared enamel data for mammals from three fossil sites aged 1.8-3.0 Ma, all of which are on dolomites, with data from modern mammals living on dolomitic and granitic substrates. Sr/Ca and Ba/Ca are about three times higher in enamel from modern mammals on granites than those living on dolomites, stressing the need for geologically appropriate modern/fossil comparisons. After pretreatment with dilute acid, we found no evidence of increased Sr/Ca, Ba/Ca, or Pb/Ca in fossil enamel. In contrast, Zn/Ca increased by over five times at one site (Makapansgat), but much more subtly elsewhere. Ecological patterning in Sr/Ca, Ba/Ca, and Sr/Ba ratios was also retained in fossil enamel. This study suggests that Sr/Ca, Ba/Ca, and Pb/Ca data likely preserve paleoecological information from these sites, but also demonstrates that geologically similar sites can differ in the degree to which they impart certain elements (Zn in this case) to fossils. Thus, screening is probably necessary on a site-by-site basis. Lastly, further investigation of elemental distributions in modern foodwebs is necessary before elemental ratio analysis can become a common tool for paleoecological reconstruction.     

Assessment of the mycoflora of commercial poultry feeds sold in the humid tropical environment of Imo State, Nigeria

This study was carried out to identify the common moulds growing in selected commercial poultry feed sold in Owerri, Imo State, Nigeria. Forty-eight bulk samples derived froml92 bags of feeds were collected from broiler starter (BS), broiler finishers (BF), grower mash (GM) and layer mash (LM) across 4 different brands of ommercial poultry feeds, which included Livestock (LF), Top (TF) Guinea (GF) and Vital (VF) feeds. The feed samples were collected during the rainy season months of June, July and August. The common moulds isolated from these feeds were Aspergillus sp., Peicillium sp.,Mucor sp., Yeast sp., Rhizopus sp., Epicoecum sp., Gymnoaseus sp., Cladosporium sp., Mortierella sp. as well as Bacteria. Generally, more organisms were isolated in June than the other months with Mortierella sp. being the only one not isolated in that month. Vital feed with 8 different isolates had the highest diversity of fungal species while the others had between 4 and 5 species. Prevalence rates across the feed types, generally ranged from 18.76% in layer mash to 30.03% in broiler finisher. The four Aspergillus sp. isolated came from GM and BF. This study highlights the need for constant monitoring of moulds in commercial feedstuff produced in the humid tropical environments such as Imo state, Nigeria. There is also the need to routinely include fungal growth nhibitors in commercial feeds since moulds are capable of reducing the nutritional values of feedstuff as well as elaborating pathogenic toxins.     

Total organic carbon in soils and its relation with manganese concentrations in soils and vegetation close to an abandoned manganese mine

This study aimed at quantifying the total organic carbon (TOC) present in soils within the proximity of the Kgwakgwe Mn oxide ore abandoned mine, Botswana, and establish its relationship with Mn concentrations in soils and vegetation based on multivariate and Geographical Information Systems (GIS) analytical techniques. Four hundred soil samples and 200 vegetation set samples were obtained from a 4 km² area close to the abandoned mine. The TOC in soil samples were determined using a carbon/hydrogen/moisture determinator, and Mn concentrations in soils and vegetation by atomic absorption spectrophotometry. Results were processed using the statistical package for social science (SPSS), GIS, and Remote Sensing (RS) techniques with the Integrated Land and Water Information System (ILWIS), Geosoft Oasis Montaj and ArcGIS software packages. The values for TOC in the soil samples from the study area ranged from 0 wt % to 7.91 wt %, with a mean of 1.90 wt %, and at the control area, from 4.07 wt % to 4.86 wt %. The range of concentrations of Mn in soils was from 36 mg/g to 24908 mg/g and for Mn concentrations in the vegetation samples from 26 mg/g to 3611 mg/g with a mean of 598 mg/g. Results of correlation coefficients depicted very weak negative association except Mn in soils/Mn in leaves which was weak but positive. The statistical data yielded four clusters as follows: cluster one consisted mainly of Mn in leaves, cluster two was constituted of Mn in soils, and cluster four had TOC. Cluster three was dominated by the three parameters but with negative t statistic. The spatial presentation of data presented revealed little or no vegetation in the south eastern area and those close to the mine workings, and some significant vegetation in the north western part of the study area. The low TOC in the soils is associated to low vegetation cover which is considered to have been influenced by the soil clay fraction mineralogy and high concentrations of Mn.     

Removal of airborne hexavalent chromium mist using chitosan gel beads as a new control approach

Airborne hexavalent chromium is a known human respiratory carcinogen and allergen. Many workers are exposed to hexavalent chromium in various processes which chromium electroplating plants are the most common. In this study, the feasibility of a new control approach to remove this pollutant using chitosan beads as a biosorbent was investigated. Hexavalent chromium sorption was studied relative to pH, pollution concentration, sorbent concentration, temperature, and air velocity using one factor at a time approach and Taguchi experimental design. Polluted air with different chromium mist concentrations (10–5000 μg/m³) was contacted to chitosan beads (3.3–20 g/L), floating in distilled water with adjusted pH (3–7), using an impinger at different temperatures (20 and 35 °C), and various velocities (1.12 and 2.24 m/s). The ANOVA test result showed that, there were statistical significant differences between factor levels except optimized pH levels. The higher ions removal efficiencies were achieved at lower levels of air velocities, pollution concentrations, and higher levels of solution pH values, temperatures, and sorbent concentrations.     

An electrochemical study of pyrite oxidation in the presence of carbon coatings in cyanide medium

The anodic and cathodic behaviour of pyrite with clay and different carbon coatings of activated carbon, graphite and carbonaceous matter in cyanide medium was investigated using the potentiodynamic method. The presence of clay coating did not change the polarisation curve appearance for either the anodic oxidation of pyrite or the cathodic reduction of oxygen or the potential of the current plateau, but only decreased the plateau current especially at a higher coating thickness. The presence of the carbon coatings marginally shifted the rest potential for pyrite to a more anodic position and slightly changed the polarisation curve appearance for pyrite oxidation. The current density for pyrite oxidation largely increased in the presence of the carbon coatings, the potential at the plateau shifted to more cathodic positions, and the plateau width became smaller. These effects became more noticeable at a higher coating thickness. The activated carbon, graphite and carbonaceous matter coatings performed similarly in affecting pyrite oxidation at a similar thickness. The carbon coatings significantly increased the limiting current densities for oxygen reduction on pyrite, and the limiting current plateau became steeper at a higher coating thickness. The carbon coatings increased the limiting current density for oxygen reduction to a similar extent at a low coating thickness, but increased to varied extents at a higher coating thickness. The carbon coatings also greatly increased the cathodic current density for gold reduction on pyrite. The enhancement of pyrite oxidation and oxygen or gold reduction on pyrite by the carbon coatings was likely attributed to the electrochemical interaction between pyrite and the carbon materials with electron-rich surfaces and high conductivity. The presence of the carbon coatings significantly increased the oxidation of pyrite in aerated cyanide solutions and the preg-robbing of pyrite especially at a higher coating thickness.